Microemulsions of aminopolysiloxanes

ABSTRACT

Aqueous microemulsions of protonated aminopolysiloxanes (α) comprising an amphoteric surfactant (β) and optionally at least one non-ionic emulsifier (γ) and optionally hydrotropics (δ) and/or cationic emulsifiers (η) and the pH of which is ≦7 are suitable as finishing agents of good stability, in particular stability to shearing forces, for the treatment of fibrous material, in particular textile material.

This is a continuation of application Ser. No. 08/171,782, filed Dec.21, 1993, now abandoned, which in turn is a division of application Ser.No. 07/878,790, filed May 5, 1992, now abandoned, which in turn is acontinuation of application Ser. No. 07/579,422, filed Sep. 7, 1990, thelatter two of which are now abandoned.

For the finishing of substrates, in particular textile material withaminopolysiloxanes a distribution as fine as possible thereof in thetreatment liquor is desired and thus aminopolysiloxanes have beenemulsified in water by means of particular techniques and/or surfactantsto form fine particle-size emulsions to microemulsions. From EP 138 192A it is e.g. known to produce such microemulsions over an oilconcentrate using defined oil-soluble surfactants and by rapid stirringof the oil-concentrates into water the particle size of the obtainedemulsion depending on the speed of dispersion. It is known that suchemulsions display the deficiencies in type-conformity and heat-stabilityindicated in EP 358 652 A. From EP 358 652 A it is known to formulateparticular aminopolysiloxanes as microemulsions by means of definedhydrosoluble, in particular nitrogen-free, emulsifiers and of acid.

The mentioned microemulsions have a certain stability. In the art, inparticular in the field of textile treatment there was, however, still aneed for aminopolysiloxane-microemulsions sufficiently stable toshearing forces in order to be stable even at very high dynamic stressof the textile treatment liquor, i.e. in order to maintain their finedistribution in the treatment liquor and consequently their efficiency(e.g. their build-up on the substrate) and in order to avoid siliconedeposits caused by destabilisation on the treated goods (which lead tothe feared silicone spots) and on parts of the assembly (which impairthe treated goods by silicone-stainings as well as the good working ofthe assembly and requires an uneconomic cleaning of the assembly).

It has now surprisingly been found that by employing amphoteric--inparticular nitrogen-containing--surfactants (β), as defined below, andadjusting the pH-value as indicated below, there may be obtained aqueousaminopolysiloxane microemulsions of high stability to shearing forces,in particular as described below.

The invention refers to aqueous emulsifier-containing microemulsions ofaminopolysiloxanes, as defined below, their production and their use.

The invention, thus, provides an aqueous microemulsion of anaminopolysiloxane (α) which is characterized by a content of anamphoteric surfactant (β) and a pH≦7.

The term microemulsion is used here in the most general meaning of theword and encompasses liquid systems in which the components aredistributed in the continuous phase so finely that they represent cleartwo-phase systems up to colloidal solutions. As microemulsions there areunderstood here in particular such that are translucent to transparent(light-transmitting to optically clear), essentially such with anaverage particle diameter (numerical average) of the dispersedparticles≦0.2 μm, preferably ≦0.1 μm, principally wherein the particlediameter of the dispersed particles is preponderantly ≦0.2 μm,preferably ≦0.1 μm.

As aminopolysiloxanes (α) are suitable in general any aminopolysiloxanesof polycationic character, essentially such that are built-up ofrepeating dimethylsiloxy units and aminosiloxy units (in particularaliphatic aminosiloxy units in which the amino groups are bound oyercarbon to Si). They may have a linear structure or even a branchedand/or cross-linked structure. The terminal groups may contain areactive substituent, e.g. --OH, or optionally be blocked; a preferredblocking terminal group is the trimethylsiloxy group.

The aminopolysiloxanes to be employed according to the invention arepreferably built-up of repeating units of the following formulae##STR1## wherein A signifies a bivalent hydrocarbon radical with 2-6carbon atoms, B signifies hydrogen C₁₋₄ -alkyl or --(CH₂)_(m) --NH₂,

m signifies 2 or 3,

Z signifies --CH₃ or --OX

and X signifies hydrogen, methyl or the link to radicals of formula (c)or (d) specified below or a polysiloxane radical of units (a) and/or(b).

The terminal groups of the aminopolysiloxane chains correspondpreferably to formulae (c) and/or (d). ##STR2## wherein Y signifiesmethyl, methoxy or hydroxy.

In formulae (b) and (d) A signifies preferably an aliphaticmonoethylenically unsaturated or preferably saturated hydrocarbonradical with 3-4 carbon atoms, in particular propylene-1,3 or2-methyl-propylene-1,3.

B signifies preferably hydrogen, aminoethyl or aminopropyl, inparticular aminoethyl.

Z signifies preferably methyl.

The aminopolysiloxanes (α) advantageously have a viscosity in the rangeof 500-30,000, principally 700-20,000, preferably 5000-15,000 cP(Brookfield rotational viscosimeter RV, spindle no. 5, 20° C.). Theamine value of the aminopolysiloxanes (α) is advantageously in the rangeof 0.1-3.0, preferably 0.3-1.2.

Schematically the aminopolysiloxanes (α) to be used according to theinvention may be represented by the following general formula ##STR3##wherein W₁ and W₂ signify each a group of formula (c) or (d), themolecule contains at least one group of formula (b) and the indexes xand y are chosen so, that the polymer displays the above indicatedamine-values and viscosities. The ratio of the number of dimethylsiloxyunits to the number of aminosiloxy units, in particular of the formula##STR4## is advantageously in the range of 3/1 to 300/1, preferably 10/1to 100/1.

The aminopolysiloxanes may be produced in a manner known per se oranalogously to known methods, e.g. by aminoalkylation of polysiloxanes,containing reactive Si-bound hydrogen atoms or principally bycopolymerization of amino group-containing silanes with non-ionic mono-or polysiloxanes, preferably with α,ω-dihydroxypolydimethylsiloxanes,advantageously of average molecular weight M_(n) in the range of 500 to10,000, preferably 1000 to 7000, or cyclic siloxanes, e.g.octamethylcyclotetrasiloxane. As aminosilanes come mainly intoconsideration aminosubstituted trimethoxysilanes ordimethoxymethylsilanes, wherein the amino group is bound to the siliconatom over carbon and corresponds mainly to the formula --A--NH--B.Preferred radicals --A--NH--B are γ-aminopropyl andγ-(β-aminoethylamino)-propyl.

Aminoalkylation may take place under conditions known per se andemploying conventional aminoalkylation agents.

Copolymerisation may be carried out in a manner known per se,principally by reaction of the reactants at mild or elevatedtemperature, in particular at temperatures in the range of 15°-180° C.,optionally in the presence of a catalyst and, if desired, using terminalblocking groups, e.g. with hexamethyldisiloxane. As catalysts there maybe employed acids (in particular acetic acid, formic acid, sulphuricacid, acid ion interchangers or trifluoromethanesulphonic acid) as wellas alkali metal or ammonium compounds, in particular alkali metal orammonium silanolates (e.g. potassium or tetramethylammonium silanolate),alkali metal hydroxides, carbonates or bicarbonates (e.g. potassiumhydroxide, sodium hydroxide or sodium bicarbonate) or furtherbenzyltrimethylammoniumhydroxide. If desired, polymerization may becarried out in the presence of an inert solvent that may then beeliminated, e.g. distilled off during polymerization or afterwards.

If for the introduction of the units of formula (b) there is employed anamino group-containing trimethoxysilane the methoxy group Z may,depending on the reaction conditions, be hydrolyzed to the hydroxy groupor also take further part in the copolymerisation so that at this site abranching of the copolymer may occur.

Depending on the chosen copolymerisation conditions the aminogroup-containing units may be statistically distributed throughout themolecule or may be terminal or may be grouped as in block-polymers oreven may crowd towards the extremities of the linear chains.

For the microemulsions of the invention those aminopolysiloxanes (α) arepreferred that have an optionally branched, prevalently linear structureof the polysiloxane backbone, preferably such in which Z signifiesmethyl. Further preferred are also those linear polymers that are notterminally blocked, essentially such in which in the groups (c) and (d)Y signifies hydroxy.

As amphoteric surfactants (β) come mainly into consideration such thatbesides a fatty radical and an anionic group (resp. acid group) containin the molecule at least one tertiary (in the dipolar form of theampholyte protonated) amino group or quaternary ammonium group,principally such as described in "Amphoteric Surfactants", SurfactantsScience Series, vol. 12 (Bernard R. Bluestein, Clifford L. Hilton, 1982)and in particular as set out in chapter 1 at pages 2-7, 16-36 and 50-59,in chapter 2 at pages 75-97, 113-119, 122-131, 133-143, 155, 159 and 160and in chapter 3 at pages 178-203, 209, 219 and 220, of which those arehere preferred that are described at pages 30, 31, 77, 78, 87, 197 and220. Advantageously there are employed as (β) such amphotericsurfactants in which (referred to the non-dipolar form of the ampholyte)the acid group is a carboxylic or sulphonic acid group and thelipophilic radical is bound over a carbamoyl group to the remaining partof the molecule or is the 2-positioned substituent of an amphotericimidazoline or of the imidazolinium ring of a betaine of theimidazolinium series. Preferably there are employed amphotericsurfactants (β) of the following formulae ##STR5## wherein R--CO--signifies the radical of a fatty acid with 8-24 carbon atoms,

n signifies a number from 2 to 6,

R₁ signifies hydrogen, C₁₋₄ -alkyl, benzyl or β-hydroxy-ethyl or-propyl,

R₂ signifies C₁₋₄ -alkyl,

R₃ signifies C₁₋₄ -alkyl, benzyl or β-hydroxyethyl or -propyl,

G signifies C₁₋₃ -alkylene or 2-hydroxy-propylene-1,3,

L signifies a carboxy- or sulphonic acid group

and Q signifies the counterion to the ammonium cation or mixturesthereof.

R in formulae (IV) and (V) corresponds in its significance to the symbolR in the formulae (II) and (III), i.e. it signifies a correspondingaliphatic hydrocarbon radical with 7-23 carbon atoms.

The quaternary imidazolinium compounds containing, besides the2-positioned radical R, the N-bound radicals R₃ and --G--L may occuroptionally also in the isomeric form ##STR6##

For the sake of simplicity they will be indicated in the following onlywith the formula (V).

R--CO-- preferably is the radical of an aliphatic fatty acid with 12-18carbon atoms and may be saturated or unsaturated. The following fattyacid radicals may be mentioned: lauroyl, palmitoyl, myristoyl, oleoyl,stearoyl, behenoyl and arachidoyl as well as the radicals of technicalfatty acids, in particular of tallow fatty acid and coconut fatty acid.

R₁ advantageously signifies methyl, ethyl or preferably β-hydroxyethyl.

R₂ preferably signifies methyl.

R₃ advantageously signifies methyl, ethyl or β-hydroxyethyl; in formula(III) preferably methyl and in formula (V) preferably β-hydroxyethyl.

G advantageously signifies methylene, ethylene or propylene-1,3 or2-hydroxy-propylene-1,3. If L signifies a carboxy group G preferablysignifies C₁₋₃ -alkylene, in particular methylene; if L signifies asulpho group then G preferably signifies C₁₋₃ -alkylene or in particular2-hydroxy-propylene-1,3.

The surfactants (β) may be employed in the form of free acids(respectively internal salts) or preferably as salts in which Lsignifies --COOM or --SO₃ M and M signifies a cation. Preferably M is analkali metal cation (in particular lithium, sodium or potassium).

As counterion Q come into consideration in general conventionalcounterions as are formed in cyclization or quaternization reactions,principally the anion of a mineral acid (e.g. chloride or sulphate) or,in particular in formula (III), advantageously also for methosulphate orethosulphate, depending on the employed quaternization agent.Surfactants of formula (II) in which n signifies 2 may be reacted tosuch of formula (IV) by cyclization reactions and, vice versa,surfactants of formula (IV) may be hydrolyzed to such of formula (II) inwhich n signifies 2.

In the microemulsions of the invention there are employed advantageously5-60, preferably 10-40, in particular 15-35 parts by weight ofamphoteric surfactant (β) for every 100 parts by weight ofaminopolysiloxane (α).

The microemulsions of the invention have a pH of 7 or less which may beadjusted by acid addition, and the aminopolysiloxanes (α) are present inthe microemulsions of the invention at least in part in protonated form.The pH values of the compositions of the invention are advantageously inthe range of pH 2-5, preferably 3-5.

As acids (ε) that may be employed for setting the pH, any sufficientlystrong acids are suitable, preferably

(ε₁) aliphatic carboxylic acids with 1-8 carbon atoms, in particularsimple carboxylic acids with 1-6, preferably 1-4 carbon atoms(principally formic acid, acetic acid, propionic acid and burytic acid),dicarboxylic acids with 2 to 6 carbon atoms (principally oxalic acid,succinic acid, glutaric acid and adipic acid) and hydroxy-carboxylicacids with 3-8, preferably 3-4, carbon atoms (principally lactic acid,tartaric acid, citric acid, gluconic acid and glucoheptic acid), andstronger acids

(ε₂) preferably mineral acids (in particular hydrochloric acid,sulphuric acid or phosphoric acid) and stronger organic acids (inparticular trichloroacetic acid and trifluoromethane sulphonic acid).

Of the acids (ε₁) formic acid and acetic acid are preferred. Of theacids (ε₂) sulphuric acid and hydrochloric acid are preferred.

The microemulsions of the invention advantageously contain at least onenon-ionic emulsifier (γ).

Suitable non-ionic emulsifiers (γ) are in particular such with an HLBvalue in the range of 5-16. The emulsifiers (γ) may be of aliphatic andoptionally also aromatic character, preferably they are, however, purelyaliphatic. Particularly worth mention are sorbitemonoesters of C₈₋₁₆-(preferably C₁₁₋₁₄ --) fatty acids and oxyethylation products of fattyalcohols or of fatty acid amides, wherein the fatty radicaladvantageously contains 8-22 carbon atoms, preferably 10-18 carbonatoms. Besides ethyleneoxy units there may optionally also be an amount,in particular a minor amount of propyleneoxy units built-in in thenon-ionic surfactant. There may be mentioned in particular oxyethylationproducts of the following fatty alcohols and fatty acid amides: laurylalcohol, myristyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcoholand technical alcohols, in particular tallow fatty alcohol and coconutfatty alcohol, as well as the analogous fatty acid amides, and little orhighly branched primary or secondary synthetic alcohols from theoxosynthesis--e.g. from propylene--of which those with 10-15 carbonatoms are preferred, mainly trimethylnonanol, tetramethylnonanol andtetramethyldecanol, in particular the primary isotridecylalcohol,tetramethylnonanol-1; among the sorbite fatty acid esters sorbitanmonolaurate is particularly preferred. The degree of oxyethylation issuitably chosen so that the desired HLB is achieved. It is of particularadvantage to use two different emulsifiers (γ) viz. mainly non-ionicemulsifiers (γ₁) with a lower HLB-value, advantageously a HLB-value inthe range of 5-12, preferably 6-12, and emulsifiers (γ₂) of higherHLB-value, advantageously in the range of 10-16, preferably 12-16, theHLB-value of (γ₂) being higher than the one of (γ₁) advantageously by atleast one unit, preferably by at least 2 units.

The HLB-values of the oxyethylation products may be calculated by meansof the known formula HLB=E/5 (E=% by weight of ethyleneoxy in themolecule).

For every 100 parts by weight of the aminopolysiloxane (α) there areemployed advantageously 10 to 60; preferably 15 to 50 parts by weight ofnon-ionic emulsifier (γ) resp. of the non-ionic emulsifier mixture(γ₁)+(γ₂). The weight ratio (γ₁): (γ₂) is advantageously in the range of1:9 to 9:1, principally 1.5:8.5 to 8.5:1.5, preferably 4:6 to 6:4.

Hydrotropics (δ) may, if desired, be employed, especially if as (γ₁)there are employed emulsifiers with an HLB >10.

As (δ) are suitable, in general, known advantageously aliphatic lowmolecular compounds, preferably non-ionic C/H/O-compounds, in particularwith 2-24 carbon atoms, principally aliphatic alcohols and/or etherswith 4-18, in particular 4-12 carbon atoms. Preferred hydrotropics arepolyols [in particular 1,3-butanediol, neopentyl glycol, pentaerythrite,1,1,1-tris(hydroxymethyl)-ethane or -propane, 2,5-hexanediol and2-methyl-pentane-2,4-diol], oligoalkylene glycols and their alkylethers[principally di-, tri- tetra-, penta- and hexaethylene glycol and mono-or di-(C₁₋₆ -alkyl)-ethers thereof, in particular di-, tri- ortetraethylene glycol monobutylether and bis-(2-hydroxypropyl)-ether, anddipropylene glycol] and glucosides that are etherified with C₁₋₆ -alkylat the anomeric hydroxy group (preferably butylglucoside).

For every 100 parts by weight of (α) there are employed advantageouslyup to 60 parts by weight, advantageously up to 50 parts by weight, inparticular 5-50 parts by weight of (δ).

The aqueous microemulsions of the invention contain advantageously up to70% by weight, principally 15-70% by weight, preferably 20-60% byweight, in particular 30-50% by weight of the total of components[(α)+(β)+(γ)+(δ)], the content of (δ) being 0-60% by weight, referred to(α).

According to a preferred aspect of the invention the microemulsions ofthe invention contain at least one cationic surfactant (η). As cationicsurfactants (η) come into consideration principally ammonium compoundsthat contain at least one lipophilic radical which is advantageously analiphatic fatty radical with 8-24 carbon atoms, the molecule containingpreferably not more than one such lipophilic radical per ammonium group.As cationic surfactant (η) come into consideration preferably such ofthe following formula ##STR7## in which T signifies a radical of formulaR'--CH₂ --, R'--CO--NH--T'-- or R'--CH₂ --O--T"--,

R' signifies an aliphatic hydrocarbon radical with 7-23 carbon atoms,

T₁ signifies C₂₋₆ -alkylene,

T' signifies C₂₋₆ -alkylene,

T" signifies C₂₋₆ -alkylene or --CH₂ --CHOH--CH₂ --,

each R₄ independently signifies C₁₋₄ -alkyl or a radical of formula--(CH₂ --CH₂ --O)_(q) --H,

each R₅ independently signifies hydrogen or C₁₋₄ -alkyl,

R₆ signifies C₁₋₄ -alkyl, a radical of formula --(CH₂ --CH₂ --O)_(q) --Hor T,

p signifies a number from 1 to 2,

each q signifies at least 1, and Σq≦70

and Q₁ signifies a counterion to the ammonium cation.

If in formula (VI) R₅ signifies hydrogen, there may be employedadvantageously the corresponding protonatable free bases of formula##STR8## which may then be protonated at latest when adjusting thepH-value to pH ≦7.

The radical R' contains advantageously 11-21 carbon atoms. As radicalsR'--CH₂ -- mainly the following come into consideration: lauryl,palmityl, cetyl, oleyl, stearyl, behenyl, arachidyl, tallow alkyl orcocoalkyl of which those with 12-18 carbon atoms are preferred. Asradicals R'--CO-- come into consideration, in particular, the acylradicals of the corresponding fatty acids, e.g. as indicated above forR--CO--.

T₁ and T' signify preferably T₂, i.e. ethylene or propylene, of whichpropylene -1,3 is particularly preferred.

T" signifies preferably ethylene, propylene or 2-hydroxypropylene-1,3.

T signifies preferably T₀, i.e. R'--CH₂ -- or R'CO--NH--T'--.

In a preferred subgroup (η₁) of the cationic surfactants (η)

R₄ signifies R₄ ', i e. methyl or ethyl,

R₅ signifies R₅ ', i.e. C₁₋₄ -alkyl, preferably methyl or ethyl,

R₆ signifies R₆ ', i.e. C₁₋₄ -alkyl, preferably methyl or ethyl and theindex p signifies p', i.e. 0 or 1, preferably 0,

Q₁ being any conventional anion, in particular as is formed byquaternization, e.g. as indicated above for Q .

In a further preferred subgroup (η₂) of the cationic surfactants (η)

R₄ signifies R₄ ", i.e. a radical of formula --(CH₂ --CH₂ --O)_(q1) --H,

R₅ signifies hydrogen,

R₆ signifies R₆ ", i.e. a radical of formula --(CH₂ --CH₂ --O)_(q1) --H,

p signifies p", i.e. 0 or 1 and q signifies q₁, i.e. at least 2 and Σq₁=5-40, preferably 8-20,

Q₁ signifying a counterion as is formed by protonation, in particular asis formed by addition of acids (ε).

Preferred amines of formula (VII) correspond to formula ##STR9##

The quaternary surfactants (η₁) correspond advantageously to the formula##STR10## preferably to the formula ##STR11##

As cationic surfactants (η) there are employed preferably quaternarycompounds (η₁) advantageously of formula (IX), preferably of formula(X), which may advantageously be blended with (η₂) resp. with theprotonatable amines of formula (VII), preferably of formula (VIII). If(η₁) is blended with (η₂) or in particular with protonatable amines offormula (VII) resp. (VIII) the weight ratio of (η₁) to (η₂) [the lattercalculated as protonatable free base of formula (VII)], preferably ofsurfactant of formula (IX) or (X) to surfactant of formula (VIII), isadvantageously in the range of 1/2 to 5/1, preferably 1/1 to 3/1.

The surfactants (η) are employed with particular advantage whenemploying surfactants (γ₁), in particular such of HLB≦9, preferablyHLB=5-9 and/or oil-soluble surfactants (γ₁), the surfactants beingdesignated here as oil-soluble if at least 1 g thereof gives in 20 g ofa clear aminopolysiloxane (α) [in the form of the free base or in a formprotonated with (ε)] at 20° C. a clear solution.

For every 100 parts by weight of (α) there are employed advantageouslyup to 30, preferably 8 to 20 parts by weight of (η). The total of[(α)+(β)+(γ)+(δ)+(η)] in the microemulsions of the invention isadvantageously in the range of 15 to 70% by weight, principally 20 to60% by weight, preferably 30 to 50% by weight, the content of (δ) being0-60% by weight and the content of (η) being 0-30% by weight.

The microemulsions of the invention may be prepared by admixing of therespective components for which (β) may be added to the non-protonatedor to the protonated form of (α) and, if required, after the addition of(β) the pH is adjusted to the desired value. The setting of the requiredor desired acidic pH-values takes place suitably by means of acidaddition, preferably by addition of (ε), in particular (ε₁) and/or (ε₂).

The adjustment of the pH-value may take place in one or even stages,i.e. by means of one or more acid additions. Preferably the pH is setfirst with (ε₁) to a value e.g. in the range of pH 3-7, advantageouslyto a weakly acidic to neutral pH, preferably 6-7; the final pH,preferably in the range of 2-5, in particular 3-5, is preferably setwith (ε₂). It is, however, also possible to operate only with (ε₁) oronly with (ε₂).

The microemulsions of the invention are preferably produced by additionof (β) and preferably (γ) [in particular (γ₁) and (γ₂)] and optionally(δ) and/or (η) and of the required quantity of water and acid (ε) to(α). The sequence of the additions is in general discretionary, so longas the respective mixtures are well stirrable. Thus, (α) may forinstance be admixed first with (γ₁) or with (δ) or with a mixture of(γ₁) and (δ) and then be further admixed with the remaining componentseither sequentially or as mixtures [e.g. (γ₂)+(β), or (γ₁)+(γ₂)+(β)] or(γ₁)+(γ₂)+(β) and optionally (δ) and/or (ε₁) may be given together into(α). Water and acid (ε₁) may be added separately or together with therespective components. (η) may be added in any stage, advantageouslyafter the other surfactants and preferably after (ε). Advantageoussequences of additions of the components (β), (γ₁), (γ₂), (ε₁) and (ε₂)to (α) may be represented by means of the following Scheme 1

    ______________________________________                                        SCHEME 1                                                                      1.       2.         3.          4.  5.                                        ______________________________________                                        α  γ.sub.1                                                                            γ.sub.2                                                                             β                                                                            ε.sub.2                           α  γ.sub.1                                                                            γ.sub.2 + β                                                                    ε.sub.2                               α  γ.sub.1 + γ.sub.2                                                            β      ε.sub.2                               α  γ.sub.1 + γ.sub.2 + β                                                   ε.sub.2                                           ______________________________________                                    

in which (ε₁) may be added in any one or more of the stages 1 to 5and/or in the intermediate stages between 1 and 2, 2 and 3, optionally 3and 4 and optionally 4 and 5, (δ), so long as it is added, may be addedin any one or more of the stages 1 to 5 and/or of the intermediatestages between 1 and 2, 2 and 3, optionally 3 and 4 and optionally 4 and5 and/or after the addition of (ε₂).

The required water may be added separately or together with one or moreof the components, advantageously with (β), (γ₂) and/or (δ). (β) isadvantageously added in the form of aqueous composition. Advantageousvariants in the sequence of the additions are in particular thefollowing:

Variant a): adding to (α) first (γ₁) then [(γ₂)+water], then (β) andthen (ε₂)

with the following subvariants for the addition of (ε₁):

a₁): addition of (ε₁) before (γ₁),

a₂): addition of (ε₁) between (γ₁) and (γ₂) or together with (γ₁) and(γ₂),

a₃): addition of (ε₁) between (γ₂) and (β) or together with (β),

a₄): addition of (ε₁) after (γ₁), (γ₂) and (β),

and the following further subvariants for the addition of (δ):

a_(w1)): (δ) before or together with (γ₁),

a_(w2)): (δ) before or together with (γ₂),

a_(w3)): (δ) before or together with (β),

a_(w4)): (δ) after (β) and before (ε₂),

a_(w5)): (δ) after (ε₂),

wherein w=1, 2, 3 or 4;

a further subvariant is (a_(w41)) for the further addition of residual(γ₁) simultaneously with/or after (β) and before (ε₂).

Variant b): adding to (α) first (γ₁) then [(γ₂)+(β)+water] and then (ε₂)

with the following subvariants for the addition of (ε₁):

b₁): (ε₁) before (γ₁),

b₂): (ε₁) between (γ₁) and [(γ₂)+(β)+water] or simultaneously with (γ₁)or [(γ₂)+(β)+water],

b₃): (ε₁) after [(γ₂)+water] and before the addition of (ε₂) or inadmixture with (ε₂),

with the following further subvariants for the supplementary addition of(δ):

b_(w1)): (δ) before (γ₁),

b_(w2)): (δ) between (γ₁) and [(γ₂)+(β)+water] or together with (γ₁) or[(γ₂)+(β)+water],

b_(w3)): (δ) after [(γ₂)+(β)+water],

(w=1, 2 or 3).

Variant c): adding to (α) a mixture of (γ₁)+(γ₂)+(β) and thereafter

with the following subvariants for the addition of (ε₁):

c₁): (ε₁) before [(γ₁)+(γ₂)+(β)],

c₂): (ε₁) together with [(γ₁)+(γ₂)+(β)],

c₃): (ε₁) after [(γ₁)+(γ₂)+(β) ] and before (ε₂),

and the following further subvariants for the supplementary addition of(δ):

c_(w1)): (δ) before [(γ₁)+(γ₂)+(β)],

c_(w2)): (δ) simultaneously with [(γ₁)+(γ₂)+(β)],

c_(w3)): (δ) after [(γ₁)+(γ₂)+(β)] and before (ε₂),

(w=1, 2 or 3).

(η) may be added in any stage, advantageously after the addition of (β),preferably after the addition of (ε₂). The required water and optionallyadditionally required water may be added in one or more stages, e.g.when following variant c), together with (γ₁), (γ₂) and (β) and/or afterthe addition of (γ₁), (γ₂) and (β) before or simultaneously with theaddition of (ε₁).

Particularly convenient sequences of the additions of (β), (γ₁), (γ₂),(ε) [optionally subdivided into (ε₁) and (ε₂)] and optionally (δ) and/or(η) [optionally subdivided into (η₁) and (η₂)] may be represented bymeans of the following Scheme 2.

    __________________________________________________________________________    SCHEME 2                                                                        2.         3.         4.                                                                              5.    6.    7.                                      __________________________________________________________________________    α                                                                         γ.sub.1                                                                            (β + γ.sub.2).sup.1                                                           δ                                                                         ε.sub.1                                                                     ε.sub.2                                                                     (η.sub.1 + η.sub.2).sup.2       α                                                                         γ.sub.1                                                                            (β + γ.sub.2 + δ).sup.1                                                 ε.sub.1                                                                 ε.sub.2                                                                     (η.sub.1 + η.sub.2).sup.2             α                                                                         γ.sub.1                                                                            (β + γ.sub.2 + δ + ε.sub.1).sup.1                               ε.sub.2                                                                 (η.sub.1 + η.sub.2).sup.2                   α                                                                         γ.sub.1 + γ.sub.2                                                            β.sup.1                                                                             δ                                                                         ε.sub.1                                                                     ε.sub.2                                                                     (η.sub.1 + η.sub.2).sup.2       α                                                                         γ.sub.1 + γ.sub.2                                                            (β + δ).sup.1                                                                 ε.sub.1                                                                 ε.sub.2                                                                     (η.sub.1 + η.sub.2).sup.2             α                                                                         γ.sub.1 + ε.sub.1                                                          (β + γ.sub.2).sup.1                                                           δ                                                                         ε.sub.2                                                                     (η.sub.1 + η.sub.2).sup.2             α                                                                         γ.sub.1 + ε.sub.1                                                          (β + γ.sub.2 + δ).sup.1                                                 ε.sub.2                                                                 (η.sub.1 + η.sub.2).sup.2                   α                                                                         γ.sub.1 + δ                                                                  (β+ γ.sub.2).sup.1                                                            ε.sub.1                                                                 ε.sub.2                                                                     (η.sub.1 + η.sub.2).sup.2             α                                                                         δ    (β + γ.sub.1 + γ.sub.2).sup.1                                           ε.sub.1                                                                 ε.sub.2                                                                     (η.sub.1 + η.sub.2).sup.2             α                                                                         γ.sub.1 + γ.sub.2 + β                                                   δ.sup.1                                                                            ε.sub.1                                                                 ε.sub.2                                                                     (η.sub.1 + η.sub.2).sup.2             α                                                                         (β + γ.sub.1 + γ.sub.2 + δ).sup.1                                 ε.sub.1                                                                          ε.sub.2                                                                 (η.sub.1 + η.sub.2).sup.2                   __________________________________________________________________________     .sup.1 Together with the main quantity of water                               .sup.2 As aqueous solution                                               

By admixing of components (α), (β), (γ₁) and (γ₂) and water as well asoptionally (δ) there may be formed, in particular under neutral to basicconditions, even at elevated temperatures, opaque emulsions(macroemulsions) which, however, upon acid addition--even only additionof (ε₁)--can be transformed into-light transmitting to clearmicroemulsions. If the form of (α) protonated with (ε) is used from thebeginning, a microemulsion may already be formed by mixing-in of (γ₁),(γ₂) and water.

The addition of the respective components may take place at any suitablespeed, i.e. an optionally aqueous component or an optionally aqueouscomponent mixture may be added rapidly and with quick stirring within afew minutes or, simplest, be mixed-in slowly during one or more quartersof an hour (e.g. during half an hour to two hours). The admixing of thecomponents may be carried out at any suitable temperatures, e.g. in therange of 15° C. to reflux temperature, advantageously from roomtemperature (=20° C.) to 80° C., temperatures <50° C. being also wellsuitable.

The microemulsions of the invention, in particular those produced asdescribed above, are suitable as finishing agents for fibrous materialand may, so as they are formulated, be directly employed for theformulation of the application liquor or may, if required, be dilutedwith water to more diluted stock dispersions, e.g. up to a dry substancecontent of 2-4% by weight before application from aqueous medium. Theaqueous compositions of the invention may if desired contain furtheradditives, such as perfumes or fungicides. They are suitable forfinishing fibrous material, in particular textile material from aqueousmedium, in particular in order to improve their handle and glidingproperties.

Any textile material as occurs in textile industry is suitable, viz. aswell as natural as synthetic and semi-synthetic materials and theirmixtures, in particular natural or regenerated cellulose, natural orsynthetic polyamide, polyester-, polyurethane- orpolyacrylonitrile-containing material and mixtures thereof (e.g. PES/COand PAN/CO). The material may be in any processing form, i.e. as loosefibers, filaments, threads, yarn skeins and spools, woven goods, knittedgoods, non-bonded or bonded non-wovens, felts, carpets, velvet, tuftingor even as half-ready or ready-made goods. Preferred substrates arecross-wound spools, open width or tubular textiles (in particulartubular knittings) or piece-goods. Finishing takes place suitably fromaqueous clearly acidic to nearly neutral medium, in particular in the pHrange of 3.0-7.5. The concentration of composition of the invention,referred to the substrates, may vary broadly, depending on the kind andconstitution of the substrate and on the desired effect, and isadvantageously--calculated on component (α)--in the range of 0.1--1,preferably 0.2--0.6% of aminopolysiloxane (α), referred to the dryweight of the substrate.

The finishing process of the invention is carried out advantageously asthe last finishing step of the material, preferably upon a bleaching, anoptical brightening process and/or a dyeing process, optionallysimultaneously with a further treatment, e.g. as permanent finishing(synthetic resin size) of the fibrous material. The finishing may becarried out according to any methods conventional per se, e.g. byimpregnation or exhaust methods. For exhaust methods procedure from longor also short liquors may come into consideration, e.g. atliquor-to-goods ratios of 1:100 to 1:0.5, in particular between 1:60 to1:2; the application temperature may range in conventional values, e.g.in the range between room temperature and 60° C., preferably in therange of 25°-40° C.; the pH value is preferably in the range of 4-6.Also impregnation may be carried out according to methods conventionalper se, e.g. by dipping, padding, foam application or spraying,preferably at temperatures of 15°-40° C. and at pH values in the rangeof 3.5-7. After the impregnation resp. after the exhaust procedure, thetreated goods may be dried in conventional way, e.g. at 30°-180° C.,preferably 60°-140° C.

The microemulsions of the invention are distinguished by an outstandingstability (in particular shear stability) and the application liquorsare stable and of unchanged efficiency, even under strong dynamic stressof liquor and/or textile material; they are therefore suitable, e.g. forthe finishing in the winch beck, in the jigger, in yarn-dyeingassemblies, in garment-dyeing machines and in particular also injet-dyeing machines, even in those in which extremely high shearingforces arise (also bound and rebound forces). The compositions of theinvention are also very well suitable for the wet-finishing ofcross-wound spools; also in this case the strong dynamic stress of theliquor which is forced from the inner of the spool outwards through theyarns of the cross-wound spool, has practically no negative effect onthe compositions of the invention and on the finishing obtainedtherewith. The compositions of the invention --in particular the(η)-containing ones--when added to the treatment liquors, are alsostable to impurities which may derive, e.g. in the form of residues,from a preceding treatment of the substrates, in particular anionicimpurities, e.g. dyestuffs, optical brighteners or surfactants.

In the following examples parts and percentages-are by weight, thetemperatures are indicated in degrees Celsius, parts by weight relate toparts by volume as g to ml.

The employed surfactants (β) are the following: ##STR12## in whichR"--CO-- signifies oleoyl and R" in (β₁) has the same significance (C₁₇H₃₃) as in (β₂), (β₃) an (β₄).

The employed emulsifiers (γ₁) and (γ₂) are the following:

(γ₁₁) addition product of 4 moles of ethyleneoxide to 1 mole oftechnical isotridecylalcohol*

(γ₁₂) addition product of 5 moles of ethyleneoxide to 1 mole oftechnical isotridecylalcohol*

(γ₁₃) addition product of 6 moles of ethyleneoxide to 1 mole of2,6,8-trimethylnonanol-4 (Tergitol TMN-6, UNION CARBIDE)

(γ₁₄) addition product of 3 moles of ethyleneoxide to 1 mole ofC₁₁₋₁₅)-alcanol (Tergitol 15-S-3)

(γ₁₅) sorbitanemonolaurate

(γ₂₁) addition product of 9.5 moles of ethyleneoxide to 1 mole oftechnical isotridecylalcohol.

* technical isomeric mixture from the oxosynthesis

The employed surfactants (η₁) and (η₂) are the following: ##STR13## inwhich C₁₇ H₃₅ --CO-- signifies the stearoyl radical, C₁₈ H₃₅ signifiesthe oleyl radical

and w+z=15.

EXAMPLE 1 (PRODUCTS A, B, C AND D)

185.4 parts of α,ω-Dihydroxypolydimethylsiloxane with a hydroxy value of26 (determined by means of the phenylisocyanate method) and an averagemolecular weight M_(n) of 5000 (determined by means of vapor-pressureosmometry) are admixed with brief stirring with 12.2 parts ofN-(β-aminoethyl)-γ-(methyldimethoxysilyl)-propylamine. 2.4 parts ofglacial acetic acid are then added and the mixture is heated under anitrogen blanket to 75° C. After 5 hours at this temperature the mixtureis cooled to 50° C., the nitrogen feed is stopped and 30 parts of (γ₁₂)are added. 480.5 parts of a solution of 30 parts of (γ₂₁) in 450.5 partsof water are subsequently added dropwise during 1 hour. When about 140.0parts of the aqueous solution have been added the emulsion becomestransparent. At 30° C. are then added 3.5 parts of acetic acid and

(for Product A) 120 parts of a 50% aqueous solution of (β₁) or

(for Product B) 120 parts of a 50% aqueous solution of (β₂) or

(for Product C)

120 parts of a 50% aqueous solution of (β₃) or

(for Product D) 120 parts of a 50% aqueous solution of (β₄).

The pH is then adjusted to 4.0 by addition of hydrochloric acid of 36.5%concentration. There are obtained transparent aminopolysiloxanemicroemulsions which are stable to shearing forces.

EXAMPLE 2 (Product E)

188.70 parts of α,ω-dihydroxypolydimethylsiloxane (as in Example 1) areadmixed with stirring with 12.50 parts ofN-(β-aminoethyl)-γ-(methyl-dimethoxysilyl)-propylamine and treated with0.07 parts of a 50% sodium hydroxide solution. The mixture issubsequently heated to 112° C. under a nitrogen blanket, 1 part byvolume of distillate being collected. After 31/2 hours the mixture iscooled to 40° C. As soon as this temperature is reached 0.02 parts ofsodium bicarbonate are added and the mixture is heated to 110° C. withvacuum (at 70 mbar). After cooling to 50° C. and relaxing with nitrogen30 parts of (γ₁₂) are added. 480 parts of a solution of 30 parts of(γ₂₁) in 450 parts of water are subsequently added dropwise during 1hour. 3 parts of glacial acetic acid, 100 parts of a 50% aqueoussolution of (β₄), 147 parts of water, 20 parts of (γ₁₃) are then furtheradded and the pH-value is adjusted to 4.0 by addition of about 20 partsof 36.5% hydrochloric acid. There is obtained an aminopolysiloxanemicroemulsion (Product E) stable to shearing forces.

EXAMPLE 3 (Product F)

200.0 parts of an aminopolysiloxane obtained by condensation of 600.0parts of α,ω-dihydroxypolydimethylsiloxane (as in Example 1) and 39.6parts of N-(β-aminoethyl)-γ-(methyldimethoxysilyl)-propylamine withaddition with 7.7 parts of glacial acetic acid as a catalyst are treatedat 50° C. with 30 parts of (γ₁₁) and 20 parts of butylmonoglucoside.480.5 parts of a solution of 30 parts of (γ₂₁) in 450.5 parts of waterare subsequently added dropwise during 1 hour. 120 parts of a 50%aqueous solution of (β₄) 138.5 parts of water and 11.0 parts of formicacid are then further added. There is obtained an aminopolysiloxanemicroemulsion (Product F) which is stable to shearing forces.

EXAMPLE 4 (Product G)

200.0 parts of an aminopolysiloxane obtained by condensation of 600.0parts of α,ω-dihydroxypolydimethylsiloxane (as in Example 1) and 39.6parts of N-(β-aminoethyl)-γ-(methyldimethoxysilyl)-propylamine withaddition of 7.7 parts of glacial acetic acid are treated at 50° C. with30 parts of (γ₁₁). 480.5 parts of a solution of 30 parts (γ₂₁) in 450.5parts of water are subsequently added dropwise during 1 hour. 3.7 partsof glacial acetic acid, 120.0 parts of a 50% aqueous solution of (β₄),87.8 parts of water, 18.0 parts of 36.5% hydrochloric acid (foradjustment of the pH-value to 4.0) and 60.0 parts of dipropylenegylcolare further added sequentially. There is obtained an aminopolysiloxanemicroemulsion (Product G) which is stable to shearing forces.

EXAMPLE 5 (Product H)

300.00 parts of α,ω-dihydroxypolydimethylsiloxane with a hydroxy valueof 26 (determined by means of the phenylisocyanate method) and anaverage molecular weight M_(n) of 5000 (determined by means ofvapor-pressure osmometry) are heated together with 19.80 parts ofN-aminoethyl-aminopropyl-methyldimethoxysilane and 3.84 parts of glacialacetic acid under vacuum to 75° C. until there is obtained a BROOKFIELDrotational viscosity in the range 30,000-40,000 cP. 3.58 parts ofpotassium hydroxide dissolved in 5.38 parts of water are then added andreaction is continued at 75° C. under a nitrogen blanket until aBROOKFIELD rotational viscosity in the range of 7000-9000 cP isachieved. At this point the heating and the nitrogen feed are stoppedand 49.00 parts of (γ₁₄) are added. An aqueous solution consisting of

762.15 parts of water

49.00 parts of (γ₂)

195.9 parts of a 50% aqueous solution of (β₄)

and 130.64 parts of an 80% aqueous butylmonoglucoside solution

is added in a regular flow. About 13.00 parts of glacial acetic acid and25 parts of 36.5% hydrochloric acid are further added in order to adjustthe pH-value to 4.0. There is obtained a transparent product that isfurther treated with 16.33 parts of (η₂₁) and 26.65 parts of (η₁₁)dissolved in 11.76 parts of water and 26.91 parts of dipropyleneglycol.There are obtained 1633.00 parts of Product H with good stability toshearing forces.

EXAMPLE 6 (Product J)

The procedure of Example 5 is repeated up to the stopping of the heatingand the nitrogen feed. At this point there are added 16.33 parts of(γ₁₄) and 32.67 parts of (γ₁₅). An aqueous solution consisting of

745.81 parts of water

49.00 parts of (γ₂₁)

195.96 parts of a 50% aqueous solution of (β₄)

and 130.64 parts of an 80% aqueous butylmonoglucoside solution

are then added in a regular flow. About 13.00 parts of glacial aceticacid and 25.00 parts of 36.5% hydrochloric acid are then further addedin order to adjust the pH to 4.0. There is obtained a transparentproduct which is further treated with 39.98 parts of (γ₁₁) dissolved in17.64 parts of water and 40.37 parts of dipropylenglycol. There areobtained 1633.00 parts of Product J with a good stability to shearingforces.

EXAMPLE 7 (Product K)

The procedure of Example 5 is repeated up to the addition of (γ₄). Anaqueous solution consisting of

729.48 parts of water

49.00 parts of (γ₂₁)

195.96 parts of a 50% aqueous solution of (β₄)

and 130.64 parts of dipropyleneglycol

are added in a regular flow. About 13.00 parts of glacial acetic acidand 25.00 parts of 36.5% hydrochloric acid are then further added inorder to adjust the pH to 4.0. There is obtained a transparent productwhich is further treated with 16.33 parts of (η₂₁) and 39.98 parts of(η₁₁) dissolved in 17.64 parts of water and 40.37 parts ofdipropyleneglycol. There are obtained 1633.00 parts of Product K with agood stability to shearing forces.

EXAMPLE 8 (Product L)

Example 7 is repeated with the difference that in place ofdipropyleneglycol there is employed 1,3-butanediol.

EXAMPLES 6bis, 7bis and 8bis (Products J', K' and L')

Examples 6, 7 reap. 8 are repeated with the difference that in place ofa solution of 39.98 parts of (η₁₁) in 17.64 parts of water and 40.39parts of dipropyleneglycol or 1,3-butenediol there is employed asolution of 39.98 parts of (η₁₁) in 58.03 parts of water. There areobtained 1633.00 parts of Product (J', K' reap. L' with good stabilityto shearing forces.

EXAMPLE 9 (Product M)

337.46 parts of octamethylcyclotetrasiloxane, 10.50 parts ofN-aminoethyl-aminopropyl-methyldimethoxyxilane and 0.75 parts of 35%solution of benzyltrimethylammoniumhydroxide in methanol are admixedtogether with stirring and heated to 80° C. After 4 hours at 80° C. themixture is heated during 30 minutes to 150° C. and after 1 hour thenon-reacted octamethyl-cyclotetrasiloxane is distilled off at 150° C.under vacuum. There are obtained 26.62 parts of distillate and 322.09parts of an amino-modified polydimethylsiloxane, which is cooled to roomtemperature. At this point there are added 32.21 parts of (γ₁₄) and thenan aqueous solution consisting of

644.18 parts of water

64.42 parts of (γ₂₁)

322.09 parts of a 50% aqueous solution of (β₄)

and 128.84 parts of an 80% aqueous butylmonoglucoside solution.

An opaque emulsion is obtained which is adjusted to pH 4.0 by means of14.82 parts of glacial acetic acid and 23.83 parts of 36.5% hydrochloricacid. The opaque emulsion is now heated to 50° C. by which a clearproduct is formed. This is now cooled to room temperature and beforedischarging 82.52 parts of a 50% solution of (η₂) in isopropanol areadded. 1633.00 parts of Product M stable to shearing forces areobtained.

Application Examples A to C

A. 1 kg of the substrate (textile material: cotton single jersey, blue)are treated at 40° C. and at a liquor-to-goods ratio of 8:1 in aLabor-jet from MATHIS (Switzerland) with 40 g of finishing agent(Products A to M). The liquor flow rate is of 60 l/min. and thetreatment duration is 20 minutes. The water has a hardness of 10° dH(according to DIN 53905) and a pH of 4. After the treatment thesubstrate is hydroextracted, dried during 90 sec. at 140° C. withouttension and tested for softness. During the treatment no deposits orsoily separations occur. No spots are detected on the textile goods.After draining-off of the liquor no deposits are observed in theassembly. All products (A-M) are stable to the shearing forces and givea clear improvement of the handle of the treated textile material (incomparison to a corresponding substrate treated without siliconemicroemulsion).

Analogously to Application Example A there are employed Products A, B,D, E, F, G, H, J, J', K, K', L L' or M instead of Product C.

B. Machine: Jet R95 from THIES, 3 chambers;

Substrate: 360 kg of polyester/cotton (50/50) single-jersey, dyed ingreen (disperse and reactive dyes)

Product: 2.0% (referred to the weight of the substrate) of Product C;

Liquor volume: 2000 l of permitite-deionized water;

Goods-to-liquor-ratio: 1:5.5;

pH-value: 4.5;

Temperature: 30° C.;

Treatment duration: 20 minutes;

Cloth running speed: 200 m/min.;

Procedure: The product pre-diluted with 150 l of the water is addedduring 5 min. No residues deposits or spots are formed. The aspect ofthe goods and the soft-handle of the dry goods are flawless.

C. Machine: 3 roll jet machine from AVESTA (Sweden);

Substrate: 150 kg of polyester/cotton (50/50) intimate blend tricot,dyed with reactive and disperse dyes (single bath two-step) andcationically aftertreated;

Product: 2.0% (based on the weight of the substrate) of Product C;

Liquor volume: 2200 l of permutite-deionized water;

Goods-to-liquor ratio: 1:15;

pH-value: 4.5;

Temperature: 30° C.;

Treatment duration: 20 min.;

Cloth running speed: 90 m/min.;

Procedure: The product pre-diluted in 150 l of the water is added during5 minutes, the temperature remaining constant. When discharging thegoods no spots or deposits are detectable on the goods or in themachine. After drying the treated goods display an excellent softhandle.

Analogously as described in Application Example B and C there areemployed Products H, J and K instead of Product C.

Analogously as on the AVESTA-jet the procedure of Application Example Cis carried out on a GASTON-COUNTY-jet.

I claim:
 1. An aqueous microemulsion of an aminopolysiloxane (α),comprising 5 to 60 pans by weight of an amphoteric surfactant (β) forevery 100 parts by weight of (α), and an acid (ε) to produce a pH≦7. 2.An aqueous microemulsion according to claim 1, wherein theaminopolysiloxane (α) has an amine value in the range of 0.1-3.0 and aviscosity in the range of 500-30,000 cP at room temperature.
 3. Anaqueous microemulsion according to claim 1, wherein the amphotericsurfactant (β) is selected from the group consisting of an amino acidwith at least one tertiary amino group and a betaine.
 4. An aqueousmicroemulsion according to claim 3, wherein the acid group in (β) is acarboxylic or sulphonic acid group; and a lipophilic radical is bridgedby a carbamoyl group to the rest of the molecule or is the 2-positionsubstituent of an amphoteric imidazoline or of the imidazolinium ring ofa betaine of the imidazolinium series.
 5. An aqueous microemulsionaccording to claim 1, containing at least one non-ionic emulsifier (γ).6. An aqueous microemulsion according to claim 5, wherein at least onenon-ionic emulsifier (γ) has an HLB in the range of 5-16.
 7. An aqueousmicroemulsion according to claim 5, containing for every 100 parts byweight of aminopolysiloxane (α) 10-60 parts by weight of nonionicemulsifier.
 8. An aqueous microemulsion according to claim 5 comprisinga hydrotropic compound (δ).
 9. An aqueous microemulsion according toclaim 1, containing at least one cationic surfactant (η).
 10. An aqueousmicroemulsion according to claim 9 containing up to 30 parts by weightof (η) for every 100 parts by weight of (α).
 11. An aqueousmicroemulsion according to claim 5 containing 15-70% by weight of[(α)+(β)+(γ)+(δ)+(η)], the content of (δ) being 0-60% by weight and thecontent of (η) being 0-30% by weight.
 12. An aqueous microemulsionaccording to claim 1 wherein any other surfactant present is cationic ornonionic.
 13. An aqueous microemulsion according to claim 5 containing anonionic emulsifier (γ₁) having an HLB-value in the range 5-12 and anonionic emulsifier (γ₂) having an HLB-value in the range 10-16, theHLB-value of (γ₂) being at least one unit higher than the HLB-value of(γ₁).
 14. An aqueous microemulsion according to claim 1 wherein theaminopolysiloxane (α) is of the general formula ##STR14## wherein W₁ andW₂ each signify a group of formula (c) or (d) ##STR15## A signifies abivalent hydrocarbon radical with 2-6 carbon atoms, B signifieshydrogen, C₁₋₄ alkyl or --(CH₂)_(m) --NH₂,m signifies 2 or 3, Zsignifies --CH₃ or --OX, X signifies hydrogen, methyl or the link toradicals of formula (c) or (d) or a polysiloxane radical of the units ineither or both sets of brackets, Y signifies methyl, methoxy or hydroxyand x and y are such that the polymers have an amine value in the range0.1-3.0 and a viscosity in the range 500-30,000 cP at room temperature,provided that y is at least
 1. 15. An aqueous microemulsion according toclaim 14 wherein, in formula I, the ratio of the number ofdimethylsiloxy units to the number of aminosiloxy units is in the range3/1 to 300/1.
 16. An aqueous microemulsion according to claim 15wherein, in formula I, A is propylene-1,3 or 2-methyl-propylene-1,3, Bis hydrogen, aminoethyl or aminopropyl and Z is methyl.
 17. An aqueousmicroemulsion according to claim 16 wherein, in formula I, A ispropylene-1,3 or 2-methyl-propylene-1,3, B is hydrogen, aminoethyl oraminopropyl and Z is methyl.
 18. An aqueous microemulsion according toclaim 13 wherein the weight ratio (γ₁):(γ₂) is in the range 1:9 to 9:1.19. An aqueous microemulsion according to claim 1, wherein theaminopolysiloxane (α) is at least in part in protonated form.
 20. Anaqueous microemulsion according to claim 19 wherein theaminopolysiloxane (α) is at least in part in protonated form.